JP2002148798A - Photosensitive resin composition and method for forming pattern by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having such properties that the composition has excellent coating property by printing and can form a fine pattern with high accuracy by printing, the composition has excellent sensitivity and resistance against sand blasting, processes of removing solvents or peeling and removing a resist pattern are not required, no calcination residue is produced during calcining, and the composition can be rapidly hardened in an exposure process, and to provide a method for forming a pattern by using the above composition. SOLUTION: The photosensitive resin composition contains (A) photopolymerizable urethane(meth)acrylate oligomers having at least two (meth) acryloyl groups, (B) an organic filler and (C) a photopolymerization initiator. The above composition is used for the method for forming a pattern.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive composition and a method for forming a pattern using the same. The present invention relates to a method for forming a used pattern.

[Prior art]

Conventionally, a sandblasting method has been known as a processing method for forming a pattern on the surface of a substrate such as glass, stone, plastic, ceramics, leather, and wood. One of the sandblasting methods is a substrate. There is a processing method in which a resist pattern made of a photosensitive composition is formed on the surface, and the substrate exposed at the opening is selectively removed by spraying an abrasive or the like. The processing method has high working efficiency and is easy to perform fine processing. For example, it is used for forming a circuit board, a metal wiring pattern and a partition pattern of a plasma display, a ceramic, an insulating pattern of a phosphor, and the like. I have.

As a method for forming the above resist pattern, for example, as described in JP-A-60-10242, a polyurethane prepolymer, a monofunctional ethylenically unsaturated compound and a photopolymerization initiator are contained. Printing by a screen printing method using a photopolymerizable composition containing no, and curing the same, and JP-A-11-119430.
As described in (1), a method of forming a photosensitive resin composition layer for sandblasting on a substrate, irradiating with an actinic ray through a mask, and developing (photolithography method) is exemplified. However, in the method of forming a resist pattern described in JP-A-60-10242, bleeding or blurring occurs during printing, and it has been difficult to form a fine pattern. On the other hand, a non-photosensitive pattern forming material in which an inorganic filler is blended with a resin component, and a method of printing the same in a pattern and forming a mask pattern have been proposed in JP-A-9-245629. In the method, bleeding or blurring occurs at the time of printing, and it is difficult to form a fine pattern. In addition, the inorganic filler is mixed after sandblasting, for example, when forming a barrier pattern of a plasma display panel (hereinafter referred to as PDP). In the case of firing, there is a problem that it remains as a firing residue and deteriorates panel discharge characteristics.

On the other hand, the photolithography method can form a resist pattern with high accuracy and is good as a means for fine processing. However, since a resist pattern is formed using a photo process, the apparatus becomes expensive and the There are drawbacks such as the necessity of processing and the step of removing the resist pattern, which increases the manufacturing cost.

[0005]

In view of the current situation,
The present inventors have conducted intensive studies, and have found that a photosensitive composition containing a photopolymerizable urethane oligomer having at least two (meth) acryloyl groups and a photopolymerization initiator further contains an organic filler, thereby obtaining a photosensitive composition. It has been found that the thixotropic properties of the photosensitive resin composition are improved and the coating properties are improved, and that the photosensitive resin composition can be prepared without a solvent and that there is no problem of solvent removal. Furthermore, the photosensitive resin composition does not require the removal and removal of the resist pattern completely volatilized or decomposed even in the firing step after sand blasting, and can be quickly cured in the exposure step and have a high precision fine pattern. The present invention has been completed by also finding that can be formed.
That is,

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive composition which is excellent in applicability by printing, can print a fine and highly accurate pattern, and has excellent sensitivity and sandblast resistance.

Further, the present invention provides a photosensitive resin composition which does not require a solvent removing step and a resist pattern peeling / removing step, does not generate a firing residue during firing, and can be rapidly cured by an exposure step. The purpose is to provide.

Another object of the present invention is to provide a method for forming a pattern using the above photosensitive composition.

[0009]

The present invention for achieving the above object comprises (A) a photopolymerizable urethane (meth) acrylate oligomer having at least two (meth) acryloyl groups, (B) an organic filler and (C) A photosensitive resin composition comprising a photopolymerization initiator and a method for forming a pattern using the same.

Hereinafter, the present invention will be described in detail. (Urethane (meth) acrylate oligomer) The photosensitive resin composition of the present invention contains (A) at least 2
A photopolymerizable urethane (meth) acrylate oligomer having two (meth) acryloyl groups (hereinafter, referred to as a component (A)), and the component (A) is a reaction product of a diol compound and a diisocyanate compound. It refers to a reaction product obtained by reacting a compound having an isocyanate group (-NCO group) at the end of a product with an acrylate compound or a methacrylate compound having a hydroxyl group or a carboxyl group. Here, the reaction product of the diol compound and the diisocyanate compound includes one in which a plurality of diol compounds are linked by urethane bonds. Since the component (A) applied to the photosensitive composition for sandblasting requires elasticity after exposure and curing, the component (A) having four or more urethane bonds in the molecule is preferable as long as the elasticity can be maintained. If the number of urethane bonds is less than 4, the sandblast resistance is extremely lowered, which is not preferable.

Examples of the diol compound forming the component (A) include polyesters and polyethers having a hydroxyl group at a terminal. These include, for example, polyesters obtained by ring-opening polymerization of lactones, polycarbonates, alkylene glycols or diol compounds obtained by a condensation reaction of a polymer thereof with a dicarboxylic acid. Examples of the lactones include δ-valerolactone, ε-caprolactone, β-propiolactone, α-methyl-β-propiolactone, β-methyl-
β-propiolactone, α-methyl-β-propiolactone, β-methyl-β-propiolactone, α, α-dimethyl-β-propiolactone, β, β-dimethyl-β
-Propiolactone and the like. As the polycarbonates, specifically, diols such as bisphenol A, hydroquinone, and dihydroxycyclohexane;
Reaction products with carbonyl compounds such as diphenyl carbonate, phosgene and succinic anhydride are exemplified. Further, examples of the alkylene glycol include, for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol, and the like. Specific examples of the polymer include addition polymerization of the alkylene glycol alone or two or more kinds. Polymers. Specific examples of the dicarboxylic acid include maleic acid, fumaric acid, glutaric acid, adipic acid and the like. Specific examples of the polyethers include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polypentamethylene glycol, and the like. 2, as a component of the polyester and the polyether,
2-bis (hydroxymethyl) propionic acid, 2,2-
Bis (2-hydroxyethyl) propionic acid, 2,2-
It is preferable to use bis (3-hydroxypropyl) propionic acid, particularly 2,2-bis (hydroxymethyl) propionic acid, because a urethane oligomer having excellent solubility in an alkaline solution can be synthesized in a removal treatment due to printing mistakes or the like. The polyesters or polyethers can be used alone or as a mixture of two or more.

Examples of the diisocyanate compound which reacts with the diol compound include dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, and 2,2-dimethylpentane.
1,5-diisocyanate, octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4-trimethylpentane-1,5-diisocyanate
Diisocyanate, nonamethylene diisocyanate,
Examples thereof include aliphatic or alicyclic diisocyanate compounds such as 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, and isophorone diisocyanate, and a single compound or a mixture of two or more compounds can be used.

Further, specific examples of the (meth) acrylate compound having a hydroxyl group or a carboxyl group which reacts with the compound having a terminal isocyanate group include hydroxymethyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl acrylate. Methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, glycerol acrylate, glycerol methacrylate, dipentaerythritol monoacrylate, dipentaerythritol monomethacrylate, acrylic acid, methacrylic acid, phthalic acid Monohydroxyethyl acrylate, ω-carboxypolycaprolactone May be mentioned acrylate, may be used that alone, or two or more kinds in combination.

The component (A) has an average molecular weight of 10
The average molecular weight is preferably in the range of 00 to 30,000.
When it is less than 00, the bonding strength of the cured film is increased, the hardness is increased, and the sandblast resistance is reduced. On the other hand, when the average molecular weight exceeds 30,000, the viscosity is increased, the coating properties are deteriorated, and the workability is deteriorated. further,
The glass transition temperature (Tg) of the component (A) is from −40 ° C. to +7.
It is preferably in the range of 0 ° C. By having a glass transition temperature in this range, sandblast resistance can be ensured, and the film does not easily volatilize or decompose during firing, leaving no fired residue. The glass transition temperature of the component (A) can be arbitrarily controlled by changing the type or composition of the monomer used for the synthesis of the component (A). The glass transition temperature (Tg) is preferably changed according to the intended use, the temperature used, and the like.

The above component (A) is used in an amount of 30 to 95 parts by mass, preferably 4 parts by mass, per 100 parts by mass of the total of components (A) to (C).
The content is preferably in the range of 0 to 90 parts by mass. If the content is less than 30 parts by mass, adhesion, elasticity and flexibility are lacking, and sandblast resistance is poor. On the other hand, if the content exceeds 95 parts by mass, the compatibility with other components decreases, and layer separation occurs during storage, which is not preferable.

(Organic Filler) The photosensitive composition of the present invention contains (B) an organic filler. As this organic filler, the thixotropic property of the photosensitive resin composition is improved,
There is no particular limitation as long as no firing residue remains in the firing step after sandblasting. For example, a filler containing a resin such as polyamide, acrylic, polyester, urethane, polyethylene, or polypropylene as a main component or a mixture thereof can be used. Above all, a filler mainly containing a polymer of an acrylic ester or a methacrylic ester is suitably used, and specific examples include a polymer mainly containing methyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate. In addition, a polymer containing styrene as a main component is preferably used. These organic fillers may be treated with a silane coupling agent, a titanium coupling agent, or the like.

The shape of the above-mentioned organic filler is preferably granular in order to improve the applicability at the time of printing, and the particle size thereof is in the range of 0.5 to 100 μm, preferably 1 to 50 μm. If the particle size is less than 0.5 μm, no improvement in coatability is observed, and if it exceeds 100 μm, the pattern resolution is undesirably reduced.

The component (B) is used in an amount of 0.4 to 35 parts by mass, preferably 5 to 50 parts by mass, per 100 parts by mass of the total of the components (A) to (C).
The content is preferably in the range of 20 parts by mass. If the content is less than 0.4 part by mass, the thixotropic property is not improved, and if the content is more than 35 parts by mass, the viscosity is increased and the printing characteristics are undesirably reduced.

(Photopolymerization initiator) As the photopolymerization initiator, known photopolymerization initiators can be used and are not particularly limited, and specific examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy -1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2,4-diethylthioxanthone, -Chlorothioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone,
Benzophenone, 1-chloro-4-propoxythioxanthone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane -1-one, 4-benzoyl-4'-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethyl 2-ethylhexyl aminobenzoate, 2-isoamyl 4-dimethylaminobenzoate, 2,2-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethylacetal, 1-phenyl-
1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone Benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldiloloacetophenone, Thioxanthone, 2-methylthioxanthone, 2
-Isopropylthioxanthone, dibenzosuberone,
α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane , 1,3-bis- (9-acridinyl) propane and the like. The photopolymerization initiators may be used alone or in combination of two or more.

The component (C) can be contained in an amount of 0.1 to 25 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the total of the components (A) to (C). The content is 0.
If the amount is less than 1 part by mass, poor exposure curing may occur, making it difficult to obtain sufficient etching resistance and chemical resistance.
If the amount is more than 1 part by mass, precipitation occurs in the composition solution, which is not preferable.

(Photopolymerizable Monomer) The photosensitive composition for sandblasting of the present invention can further contain a photopolymerizable monomer as required for further improving sensitivity and adjusting viscosity. As the photopolymerizable monomer, the above (meth)
Acrylic acid esters, ethylenically unsaturated carboxylic acids, and other monomers exemplified as copolymerizable monomers can also be used, but preferably a monomer having at least one polymerizable ethylenically unsaturated bond (hereinafter, a polyfunctional monomer) Is good). Examples of the polyfunctional monomer, for example, ethylene glycol, diacrylate or dimethacrylate of alkylene glycol such as propylene glycol, polyethylene glycol, diacrylate or dimethacrylate of polyalkylene glycol such as polypropylene glycol, glycerin, trimethylolpropane, Examples thereof include polyacrylates or polymethacrylates of trihydric polyhydric alcohols such as pentaerythritol and dipentaerythritol, and modified products of dicarboxylic acids thereof. Specific examples include ethylene glycol diacrylate, ethylene glycol dimethacrylate, and triethylene glycol. Diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol Dimethacrylate,
Propylene glycol diacrylate, propylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate,
Tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate,
Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like can be mentioned.

The above photopolymerizable monomers are (A) to (C)
It is preferable to mix the components in an amount not exceeding 60 parts by mass with respect to 100 parts by mass of the total of the components. If the amount is more than 60 parts by mass, the elasticity of the photosensitive resin composition after curing by irradiation with actinic rays will decrease, and the sandblast resistance will decrease. In addition, the viscosity of the photosensitive resin composition decreases, and the printing characteristics decrease, which is not preferable.

In the photosensitive resin composition of the present invention, in addition to the above components, a dye, a polymerization inhibitor, a cationic, anionic or amphoteric surfactant or the like can be appropriately added.

The photosensitive composition of the present invention is applied to the photosensitive resin layer by a method such as printing on a substrate in a liquid state, or applying and curing a photosensitive film formed by applying and curing a flexible film. It is formed. In particular, when precision processing is required, such as in the production of electronic components, it is preferable to use a printing method in a liquid state. Examples of the printing method include a screen printing method, an intaglio printing method, an intaglio offset printing method, a lithographic offset printing method, a letterpress printing method, a letterpress offset printing method, and the like, and the screen printing method is particularly preferable. When the screen printing method is used, the screen used is 100 to 5
About 00 mesh is preferable. Examples of the substrate include glass, ceramics, plastic, and glass provided with a thick film layer such as a rib forming layer.

The thickness of the photosensitive composition layer provided on the substrate is preferably in the range of 3 to 50 μm after curing. If the film thickness after curing is smaller than the above range, resistance during processing is poor, and it is difficult to form a highly accurate pattern, which is not preferable. On the other hand, if it is larger than the above range, the edge accuracy of the pattern is reduced and the uniformity of the film thickness is reduced. The photosensitive resin composition layer is then exposed to actinic rays and exposed to form a fine resist pattern. The exposure light used is excimer laser, X-ray,
Examples include an electron beam, and a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and the like can be used. After this exposure,
When a photosensitive film is used, development processing is performed, but a blast material is sprayed on the substrate having the opening of the obtained resist pattern exposed, and the substrate is polished and removed to form a desired pattern. As the blast material to be used, 2 to 50
0 μm glass beads, SiC, SiO ₂ , Al ₂ O, Z
Inorganic fine particles such as rO or organic fine particles such as organic plastic are suitable.

The photosensitive resin composition of the present invention is particularly useful for PDP.
It can be suitably used in the production of, and one step of the production is shown below.

(I) Formation of a rib forming layer A paper in which an inorganic powder and a vehicle are dispersed on a substrate such as glass is used.
The paste is applied and dried to form a rib forming layer. Said nothing
Machine powders include lead borate glass and zinc borate glass.
Etc. Si, B, Pb, Na, K, Mg, Ca, Ba, T
Glasses composed of various oxides such as i, Zr, Al, etc., oxidation
Cobalt, iron oxide, chromium oxide, nickel oxide, oxidation
Copper, manganese oxide, neodymium oxide, vanadium oxide,
Cerium oxide, chipeque yellow, cadmium oxide,
Lumina, silica, magnesia, spinel, Y_TwoSiO_Five:
Ce, CaWO_Four: Pb, BaMgAl₁₄O_{twenty three}: Eu,
ZnS: (Ag, Cd), Y_TwoO_Three: Eu, Y_TwoSiO_Five:
Eu, Y_ThreeAl_FiveO₁₂: Eu, Zn_Three(PO_Four)_Two: Mn,
YBO_Three: Eu, (Y, Gd) BO_Three: Eu, GdB
O_Three: Eu, ScBO_Three: Eu, LuBO_Three: Eu, Zn_Two
SiO_Four: Mn, BaAl₁₂O ₁₉: Mn, SrAl₁₃O
₁₉: Mn, CaAl₁₂O₁₉: Mn, YBO_Three: Tb, B
aMgAl₁₄O_{twenty three}: Mn, LuBO_Three: Tb, GdB
O_Three: Tb, ScBO_Three: Tb, Sr₆Si_ThreeO_ThreeCl_Four: E
u, ZnO: Zn, ZnS: (Cu, Al), ZnS:
Ag, Y_TwoO_ThreeS: Eu, ZnS: Zn, (Y, Cd) B
O_Three: Eu, BaMgAl₁₂O_{twenty three}: Fluorescent material such as Eu,
Conductive particles of iron, nickel, copper, aluminum, silver, gold, etc.
Child. In addition, as a vehicle,
Carboxymethylcellulose, hydroxyethyl cellulose
Lulose, hydroxypropylcellulose, methylcell
Loin, ethylcellulose, ethylhydroxyethyl
High content of cellulose, carboxymethyl ethyl cellulose, etc.
And linear (meth) acrylic copolymers
You.

(Ii) Formation of a resist pattern The photosensitive resin composition of the present invention in a liquid state is printed on the rib forming layer by a printing method, preferably a screen printing method, to form a photosensitive resin composition layer. Irradiation with actinic rays and curing to obtain a predetermined rib defining resist pattern. A blast material is sprayed onto the rib forming layer with the opening exposed through the resist pattern, and is selectively ground and removed to form a rib pattern such as a barrier rib or a priming rib.

(Iii) Production of PDP The substrate on which the rib pattern is formed is fired at a temperature of 500 ° C. or more to obtain ribs, and then a phosphor layer or an electrode layer is provided in the cell or between the lines, and discharge is performed. PD with gas
Produce P.

[0030]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0031]

EXAMPLES Example 1 Reactive monomer 2-methacryloyloxyethyl-
50 parts of 2-hydroxypropyl phthalate (Light ester HO-MPP, manufactured by Kyoeisha Chemical Co., Ltd.), 2-methyl- [4- (methylthio) phenyl] -2-, which is a photopolymerization initiator
4 parts of morpholino-1-propanone (Irgacure 907, manufactured by Ciba Geigy), 0.4 parts of diethylthioxanthone (Kayacure DETX, manufactured by Nippon Kayaku), 1 silicone-based antifoaming agent (KP-330 manufactured by Shin-Etsu Chemical) as an antifoaming agent
Part was stirred and dissolved, and the Tg of the cured film was -39 ° C.
OB) 50 parts and 25 parts of an organic filler (Julima MB-1X, particle size 8 μm, manufactured by Nippon Pure Chemical Co., Ltd.) containing polymethyl methacrylate as a main component were added and mixed with a stirrer to prepare a photosensitive composition.

The photosensitive composition was printed on a soda glass substrate using a screen mesh having a resolution pattern of 100 μm (pitch: 300 μm) so that the film thickness after curing became 15 μm. Exposure was performed using a high-pressure mercury lamp (1 kW) at an intensity of 1 J / cm ² , followed by curing to form a resist pattern. The obtained resist pattern has no bleeding or blurring due to printing,
The pattern size was 102 μm. Abrasive material SiC (# 600) was blasted from above the resist pattern with a blast pressure of 2.
94 × 10 ⁵ Pa (3 kgf / cm ² ), nozzle distance 80
After spraying and sandblasting at 10 mm
The temperature was raised to 550 ° C. at a temperature raising speed of min, and then cooled. The obtained soda glass substrate was cut by 150 μm, and the pattern was substantially rectangular. The pattern width was 99 μm, and no organic residue was found on the uncut soda glass substrate.

Example 2 Polypropylene glycol diacrylate as a reactive monomer (Aronix, M-22, manufactured by Toagosei Chemicals Co., Ltd.)
5) 50 parts, 2-methyl- [4-
(Methylthio) phenyl] -2-morpholino-1-propanone (Circa Geigy, Irgacure 907) 5
Part, diethylthioxanthone (Nippon Kayaku, Kayacure DETX) 0.4 part, and silicone defoamer (Shin-Etsu Chemical, KP-330) 1 part as a defoaming agent were stirred and dissolved, and the Tg of the cured film was 52. 50 ° C., 50 parts of a urethane oligomer (purchased from Nippon Synthetic Chemical Co., purple light UV-7000B), an organic filler containing polymethyl methacrylate as an organic filler as a main component (manufactured by Nippon Pure Chemical, Julimer MB-1X,
(Particle size 8 μm) was added and mixed with a stirrer to prepare a photosensitive composition.

On the other hand, a rib composition for PDP comprising an inorganic filler and ethyl cellulose having a film thickness of 15
A rib forming layer is provided by laminating the photosensitive composition to a thickness of 0 μm, and the prepared photosensitive composition is cured on the rib forming layer to a thickness of 100 μm (pitch: 300 μm) to a thickness of 15 μm.
Using a screen mesh having a resolution pattern of
Immediately print a pattern and use a UV lamp (ultra-high pressure mercury lamp 1k
Exposure was performed using W) at an intensity of 500 mJ / cm ² and cured to form a resist pattern. The obtained resist pattern had no bleeding or blurring due to printing, and the dimension of the pattern was 103 μm.

An abrasive (S) is applied over the resist pattern.
-4 # 600) at a blast pressure of 1.96 × 10 ⁵ Pa (2
kgf / cm ² ), sand blasting at a nozzle distance of 80 mm, and 550 at a heating rate of 10 ° C./min.
C. and then cooled. The rib composition for PDP was cut at the top of 100 μm and the bottom at 140 μm, and the resulting pattern was formed in a substantially rectangular shape. And
The pattern width was 98 μm, and no organic residue was found on the rib pattern.

Example 3 Example 1 was repeated, except that the organic filler used in Example 1 was replaced with an organic filler (Durima MB-SX, manufactured by Nippon Pure Chemical Industries, Ltd.) having a particle size of 4 μm and containing polymethyl methacrylate as a main component. A photosensitive composition was prepared in the same manner as described above.

Next, a resist pattern was formed in the same manner as in Example 1. The obtained resist pattern has no bleeding or blurring due to printing, and the pattern size is 1
01 μm. Further, a soda glass substrate was processed by sand blasting in the same operation as in Example 1. The obtained soda glass substrate was cut by 150 μm, and the pattern was substantially rectangular. And the pattern width is 97μ
m, and no organic residue was observed on the uncut soda glass substrate.

Comparative Example 1 The organic filler Julimer MB-1X was changed to an inorganic filler (Aerosil 380, manufactured by Nippon Aerosil)
Three rolls (M-80, manufactured by Nagase Screen Printing Laboratory)
A photosensitive composition was prepared in the same manner as in Example 1 except for kneading using S).

The above photosensitive composition was coated at 100 μm (pitch 3).
(00 μm) using a screen mesh having a resolution pattern of 15 μm
Immediately, the resist was exposed to 1 J / cm ² using a UV lamp (ultra high pressure mercury lamp 1 kW) and cured to form a resist pattern. The obtained resist pattern had no bleeding or blurring due to printing, and the pattern size was 102 μm.

An abrasive Si is formed through the resist pattern.
C (# 600), blast pressure 2.94 × 10 ⁵ Pa (3
kgf / cm ² ), sand blasting at a nozzle distance of 80 mm, and 550 at a heating rate of 10 ° C./min.
C. and then cooled. 1 for soda glass substrate
It was cut by 50 μm, and the obtained pattern was almost rectangular. Although the pattern width was 99 μm, a large number of inorganic residues (Aerosil) were found on the uncut soda glass substrate.

Comparative Example 2 The organic filler Julimer MB-1X was changed to an inorganic filler (Aerosil 380, manufactured by Nippon Aerosil Co., Ltd.)
Three rolls (M-80, manufactured by Nagase Screen Printing Laboratory)
A photosensitive composition was prepared in the same manner as in Example 2 except that the mixture was kneaded using S).

The above photosensitive composition was coated at 100 μm (pitch: 3).
(00 μm), using a screen mesh having a resolution pattern of 500 μm / cm ² using a UV lamp (ultra high pressure mercury lamp 1 kW) and immediately printing a pattern on the rib forming layer so that the film thickness after curing becomes 15 μm. The resist was exposed to light and cured to form a resist pattern.

The abrasive (S-4 # 600) was blasted at a pressure of 1.96 × 10 ⁵ Pa through the obtained resist pattern.
(2 kgf / cm ² ), sand blasting was performed at a nozzle distance of 80 mm, and then the temperature was raised to 550 ° C. at a rate of 10 ° C./min, and then cooled. The rib composition layer for PDP was cut at a top of 100 μm and a bottom of 140 μm, and the obtained pattern was formed in a substantially rectangular shape, and the pattern width was 98 μm. However, many inorganic residues (Aerosil) were found on the rib pattern. Was done.

[0044]

The photosensitive composition of the present invention has high elasticity and flexibility, is excellent in sand blast resistance, is excellent in applicability by printing, can print a fine and highly accurate pattern, and can remove solvent and resist pattern. It is a photosensitive composition that does not require a stripping / removing step, does not generate a firing residue during firing, and can be quickly cured by an exposure step. By using the photosensitive resin composition, for example, PD
A fine pattern requiring high precision, such as a partition wall pattern of P, can also be favorably formed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03F 7/40 521 G03F 7/40 521 F-term (Reference) 2H025 AA00 AA01 AB15 AC01 AD01 BC14 BC45 CA01 CA27 CC08 FA03 FA17 FA29 FA42 2H096 AA00 AA26 BA05 BA20 HA01 HA30 JA04 4J011 PA52 PB06 PB22 PC02 PC08 QB24 RA19 SA03 SA04 SA05 SA06 SA14 SA15 SA16 SA17 SA18 SA20 SA22 SA23 SA24 SA25 SA26 SA27 SA28 SA29 SA32 SA33 SA34 SA42 SA64 SA78 SA61 TA06 UA01 VA01 WA01 4J027 AG01 AG03 AG04 AG09 AG24 AG27 BA19 BA20 BA21 BA24 BA26 BA27 BA28 CA01 CA36 CB10 CC05 CD10

Claims (4)

[Claims] 1. A composition comprising (A) a photopolymerizable urethane (meth) acrylate oligomer having at least two (meth) acryloyl groups, (B) an organic filler, and (C) a photopolymerization initiator. Photosensitive resin composition. 2. The organic filler has a particle size of 0.5 to 100 μm.
The photosensitive resin composition according to claim 1, wherein 3. A resist pattern is formed on a substrate using the photosensitive resin composition according to claim 1 or 2,
A pattern forming method, wherein a substrate exposed in an opening of a pattern is ground and removed by sandblasting. 4. A resist pattern is printed on a substrate in a mask pattern using the photosensitive resin composition according to claim 1 or 2 and irradiated with actinic rays to form a resist pattern. A method for forming the described pattern.